Hemilabile Thio– and Selenoethers in Bis(benzimidazolyl)Amine Copper Complexes Relevant to the Active Sites of Copper-Dependent Monooxygenases
Por:
Sánchez-Eguía B.N., Hernández-Toledo H., Lidin S., Flores-Alamo M., Nordlander E., Bertaina S., Orio M., Castillo I.
Publicada:
1 ene 2025
Resumen:
Copper complexes supported by benzimidazole-based tetradentate neutral ligands featuring thio- and selenoether donors, resemble the coordination environment of the active site in copper dependent monooxygenases Dopamine-ß-monooxygenase (DßM) and peptidylglycine-a-hydroxylating monooxygenase (PHM). The cuprous complexes react with O2 at low temperature generating a reactive copper-oxygen species assigned to a side-on cupric–superoxo complex, which activates the C-H bond of dihydroanthracene. Based on structural, 1H and 77Se NMR, and EPR spectroscopic characterization, together with DFT computations, the selenoether moiety likely acts as a hemilabile ligand in these scaffolds, which results in an electrophilic cupric–superoxide intermediate poised for H-atom transfer, as has been proposed for related bis(benzimidazole)-thioether analogues and selenoether-modified enzymatic systems. © 2024 The Author(s). ChemCatChem published by Wiley-VCH GmbH.
Filiaciones:
Sánchez-Eguía B.N.:
Facultad de Química, División de Estudios de Posgrado, Universidad Nacional Autónoma de México, CU, Circuito Exterior, 04510, Mexico
Hernández-Toledo H.:
Instituto de Química, Universidad Nacional Autónoma de México, CU, Circuito Exterior, 04510, Mexico
Lidin S.:
Center for Analysis and Synthesis, Lund University, Lund, 221 00, Sweden
Flores-Alamo M.:
Facultad de Química, División de Estudios de Posgrado, Universidad Nacional Autónoma de México, CU, Circuito Exterior, 04510, Mexico
Nordlander E.:
Chemical Physics, Department of Chemistry, Lund University, Box 124, Lund, 221 00, Sweden
Bertaina S.:
CNRS, Aix-Marseille Université, IM2NP (UMR 7334), Institut Matériaux Microélectronique et Nanosciences de Provence, Marseille, France
Orio M.:
Institut des Sciences Moléculaires de Marseille, Aix Marseille Université, UMR 7313, Avenue Escadrille Normandie-Niémen, Marseille Cedex 20, Marseille, 13397, France
Castillo I.:
Instituto de Química, Universidad Nacional Autónoma de México, CU, Circuito Exterior, 04510, Mexico
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